1. Field of the Invention
This invention relates to Group Transfer Polymerization, to selected polyenoate compounds which are useful as monomers therein, and to selected polyenolate compounds which are useful as initiators therein.
2. Background
U.S. Pat. Nos. 4,414,372,; 4,417,304; 4,508,880; 4,524,196; 4,581,428; 4,588,795; 4,598,161; 4,605,716; 4,622,372; 4,656,233; 4,681,918; and 4,711,942; and commonly assigned U.S. patent application Ser. No. 004,831 filed Jan. 13, 1987 as a continuation-in-part of application Ser. No. 872,610 filed June 10, 1986 and expressly abandoned, referred to hereinafter as "the aforesaid patents and patent applications", disclose processes for polymerizing an acrylic or maleimide monomer to a "living" polymer in the presence of:
(i) an initiator having at least one initiating site and which is a tetracoordinate organo(Si, Sn or Ge) compound, including such compound having at least one oxygen, nitrogen or sulfur atom attached to the Si, Sn or Ge; and
(ii) a co-catalyst which is a source of fluoride, bifluoride, cyanide or azide ions or a suitable Lewis acid, Lewis base or selected oxyanion. Such polymerization processes have become known in the art as Group Transfer Polymerization (Webster et al., "Group Transfer Polymerization--a New and Versatile Kind of Addition Polymerization", J. Am. Chem. Soc. 105, 5706 (1983)).
Preferred monomers for use in Group Transfer Polymerization, hereinafter referred to as "Group Transfer Polymerization acrylic monomer(s)", are selected from acrylic and maleimide monomers of the formula CH.sub.2 .dbd.C(Y)X and ##STR1## wherein: X is --CN, --CH.dbd.CHC(O)X' or --C(O)X';
Y is --H, --CH.sub.3, --CH or --CO.sub.2 R, provided, however, when X is --CH.dbd.CHC(O)X', Y is --H or --CH.sub.3 ; PA1 X' is --OSi(R.sup.1).sub.3, --R, --OR or --NR'R"; PA1 each R.sup.1, independently, is a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms or --H, provided that at least one R.sup.1 group is not --H; PA1 R is: PA1 each of R' and R" is independently selected from C.sub.1-4 alkyl. PA1 each Q', independently, is selected from --R.sup.1, --OR.sup.1, --SR.sup.1 and --N(R.sup.1).sub.2 ; PA1 Z is an activating substituent selected from the group consisting of PA1 --CN, ##STR2## --SR.sup.6, --OP(NR'R").sub.2, --OP(OR.sup.1).sub.2, --OP[OSi(R.sup.1).sub.3 ].sub.2 and mixtures thereof; PA1 X.sup.2 is --OSi(R.sup.1).sub.3, --R.sup.6, --OR.sup.6 or --NR'R"; PA1 R.sup.6 is PA1 each of R.sup.2 and R.sup.3 is independently selected from --H and a hydrocarbyl or polymeric radical, defined as for R.sup.6 above, subparagraphs (a) to (e); PA1 R', R", R.sup.1 and Z' are as defined above for the monomer; PA1 m is 2, 3 or 4; PA1 n is 3, 4 or 5; PA1 Z.sup.1 is ##STR3## wherein R.sup.2 and R.sup.3 are as defined above; R.sup.2 and R.sup.3 taken together are ##STR4## provided Z is ##STR5## X.sup.2 and either R.sup.2 or R.sup.3 taken together are ##STR6## provided Z is ##STR7## and M is Si, Sn, or Ge. PA1 X.sup.1 is --N-- or --CH, provided, however, when the monomer is a nitrile, X.sup.1 is --CH PA1 each R.sup.4, independently, is: PA1 each R.sup.5 is --CH.sub.2 CH.sub.2 -- or --CH.sub.2 CH.sub.2 -- containing one or more alkyl or other substituents that are unreactive under polymerizing conditions. PA1 R.sup.2 is: PA1 each of R.sup.3, R.sup.4 and R.sup.5, independently, is --H or a radical as defined in (b), (c), (d) and (e) for R.sup.2 ; or R.sup.2 and the closest R.sup.4, or R.sup.3 and the closest R.sup.5, or the two closest R.sup.4 groups, or the two closest R.sup.5 groups, taken together, form a ring structure containing at least 5 carbon atoms or at least 5 carbon atoms and a heteroatom selected from --O--, --N-- and --S--, the heteroatom --N-- being substituted with R' defined as below; PA1 X is --OR or --NR'R"; PA1 R is a radical as defined in (b), (c), (d) and (e) for R.sup.2 ; or R and the closest R.sup.5, taken together, form a 5- to 8-membered lactone ring; PA1 each of R' and R", independently, is C.sub.1-4 alkyl; and PA1 n is an integer and is at least 1; provided, however: PA1 Q.sup.1 is --C(R.sup.5).dbd.C(OM[R.sup.1 ].sub.3)X'; PA1 Q.sup.2 is --C(R.sup.2).dbd.C(X')OM[R.sup.1 ].sub.3 or --R.sup.2 ; PA1 X' is --OSi(R.sup.1).sub.3, --R, --OR or --NR'R"; PA1 each R.sup.1, independently, is a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic, or mixed aliphatic-aromatic radical containing up to 20 carbon atoms; and PA1 M is Si, Sn or Ge; PA1 X' is --OSi(R.sup.1).sub.3, --R, --OR or --NR'R"; and PA1 M, R, R.sup.1-5, R', R", X and n are defined as above;
(a) a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms; PA2 (b) a polymeric radical containing at least 20 carbon atoms; PA2 (c) a radical of (a) or (b) containing one or more ether oxygen atoms within aliphatic segments thereof; PA2 (d) a radical of (a), (b) or (c) containing one or more functional substituents that are unreactive under polymerizing conditions; or PA2 (e) a radical of (a), (b), (c) or (d) containing one or more reactive substituents of the formula --Z'(O)C--C(Y.sup.1).dbd.CH.sub.2 wherein Y.sup.1 is --H or --CH.sub.3 and Z' is O or NR' wherein R.sup.40 is as defined below; and PA2 (a) a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms; PA2 (b) a polymeric radical containing at least 20 carbon atoms; PA2 (c) a radical of (a) or (b) containing one or more ether oxygen atoms within aliphatic segments thereof; PA2 (d) a radical of (a), (b) or (c) containing one or more functional substituents that are unreactive under polymerizing conditions; or PA2 (e) a radical of (a), (b), (c) or (d) containing one or more initiating sites; PA2 (a) a C.sub.1-12 alkyl, C.sub.4-12 cycloalkyl, C.sub.6-12 aralkyl or di(C.sub.1-4 alkyl)amino group; PA2 (b) a group of (a) wherein two or three of the alkyl, cycloalkyl and/or aralkyl groups are joined together by means of one or more carbon-carbon bonds; PA2 (c) a group of (a) or (b) wherein the alkyl, cycloalkyl and/or aralkyl groups contain within aliphatic segments thereof one or more hetero atoms selected from O, N and S; or PA2 (d) a group of (a), (b) or (c) wherein the alkyl, cycloalkyl and/or aralkyl groups contain one or more substituents that are unreactive under polymerizing conditions; and PA2 (a) --H or --C(O)X; PA2 (b) a hydrocarbyl radical which is an aliphatic, alicyclic, aromatic or mixed aliphatic-aromatic radical containing up to 20 carbon atoms; PA2 (c) a polymeric hydrocarbyl radical containing at least 20 carbon atoms; PA2 (d) a radical of (b) or (c) containing one or more ether oxygen atoms within aliphatic segments thereof; or PA2 (e) a radical of (b), (c) or (d) containing one or more functional substituents that are inert under polymerizing conditions; PA2 (i) when n is 1, at least one of R.sup.2, R.sup.4 and R.sup.5 is hydrocarbyl; PA2 (ii) the number of R.sup.2-5 hydrocarbyl substituents does not exceed the number of --C.dbd.C-- double bonds; PA2 (iii) a carbon atom substituted with R.sup.2-5 hydrocarbyl is not adjacent to more than one other carbon atom substituted with R.sup.2-5 hydrocarbyl, hydrocarbyl in (i), (ii) and (iii) being as defined above in (b), (d) and (e) for R.sup.2 ;
Preferred initiators are selected from tetracoordinate organsilicon, organotin and organogermanium compounds which may be represented by the formulas Q.sub.3 'MZ, Q.sub.2 'M(Z.sup.1).sub.2 and [Z.sup.1 (Q').sub.2 M].sub.2 O wherein:
Preferred initiators are those wherein M is Si.
Preferred co-catalysts are selected from a source of bifluoride ions HF.sub.2.sup.- ; a source of fluoride, cyanide or azide ions; a source of oxyanions, said oxyanions being capable of forming a conjugate acid having a pKa (DMSO) of about 5 to about 24; a suitable Lewis acid, for example, zinc chloride, bromide or iodide, boron trifluoride, an alkylaluminum oxide or an alkylaluminum chloride; or a suitable Lewis base, for example, a Lewis base of the formula selected from (R.sup.4).sub.3 M' and ##STR8## wherein: M' is P or As;
Additional details regarding Group Transfer Polymerization can be obtained from the aforesaid patents and patent applications, the disclosures of which are hereby incorporated by reference.
Numerous polyenoates containing two or more conjugated double bonds are disclosed in the art. Silyl enolates containing up to three conjugated double bonds are also known, and polyunsaturated silyl enolate initiators for "living" polymerization are generically disclosed in the aforesaid patents and patent applications. Polymers of conjugated polyenoates prepared by conventional polymerization methods are also known in the art, and the preparation of "living" polymers from polyenoate monomers by silicon-initiated polymerization is disclosed in the aforesaid patents and patent applications, the polyenoate monomers being of the formula CH.sub.2 .dbd.C(Y)CH.dbd.CHC(O)X' wherein Y is H, CH.sub.3, CN or CO.sub.2 R and X' includes OR wherein R is defined as above.
It is an object of the present invention to provide processes for preparing internally and/or terminally unsaturated "living" polymers by polymerizing one or more selected polyenoate monomers in the presence of a tetracoordinate organosilicon, organogermanium or organotin initiator and suitable co-catalyst. A further object of the invention is to provide polyenoate initiators and polyenoate monomers which are useful in Group Transfer Polymerization. Another object of this invention is to provide "living" polymers, solutions, coatings and shaped articles prepared therefrom, processes for quenching the "living" polymers, and solution or dispersion coatings and adhesives and shaped articles prepared from the quenched polymers. These and other objects will become apparent from the following description of the invention.